Disazo orange dye



United States Patent This invention relates to a new group of organiccompounds that are useful as dyes. The new compounds have the followingstructure:

wherein R represents -H or Cl ortho or para to the azo linkage, R and Rrepresent --CH or H and R represents a benzene sulfonic ester radical 0or p to the azo linkage selected from the group 'ice compounds of thisinvention can be prepared and used. In these examples, unless otherwiseindicated, parts are by weight; temperatures are given by degreescentigrade and percentages are percentages by weight.

Example 1 Metanilic acid (17.3 parts) was dissolved in 150 parts ofwater by addition of 6 parts of sodium carbonate and the resultantsolution was iced to 0. Addition of 25 parts of concentratedhydrochloric acid and 7 parts of sodium nitrite as 30% solution gave thediazonium salt. A solution of 14.3 parts of alpha-naphthylarnine in 300parts of water containing parts of concentrated hydrochloric acid wasadded, together with sufiicient ice to maintain the temperature of thecoupling at 5-10. Sodium hydroxide solution (50%) was then added slowlywith good stirring to raise the pH of the coupling to 4.5. Sodiumchloride sutficient to equal by weight of the coupling volume was addedand, after stirring minutes, more sodium hydroxide was added graduallyto It will be understood that the compounds of this invention not onlyinclude the free acids but also the water soluble salts thereof.

The new compounds are obtained by coupling metanilic or chlorometanilicacids to a-naphthylamine, rediazotizing the reaction product andcoupling the resulting diazonium salt to phenol, cresol or xylenol andthen treating the reaction product with p-toluene sulfonyl chloride,benzene sulfonyl chloride, or p-chlorobenzene sulfonyl chloride andrecovering the dye from the reaction mass.

The compounds prepared in accordance with the invention have unique andhighly valuable properties when used as dyes. They will dye polyurethanefibers and natural and synthetic polyamide fibers such as nylons, silkand wool in lighttast orange shades having a very high degree ofwashfastness even without afiteretreatments with fixatives. Thecompounds of this invention are especially useful as providing theorange component in blend colors and are particularly useful incompounding black shades for polyamide fibers. On such type of blend isdisclosed in my co-pending application Serial No. 328,051

raise the coupling pH to 10.5. Sodium nitrite (7.7 parts) as 30%solution was added, followed by 50 parts of concentrated hydrochloricacid at 510. The slurry was allowed to stir 4 hours at this temperatureto complete diazotization. The precipitate of diazonium salt was thenfiltered. The filter cake was reslurried in 30 parts of ice and 500parts of cold water, and excess nitrous acid was removed by the additionof sulfamic acid. Phenol 11.1 parts of was added to the slurry, and thena solution of 20 parts of sodium carbonate in parts of water was added,together with suflicient ice to maintain the temperature at 510. Afterstirring overnight, 4 parts of sodium hydroxide and 5 parts of sodiumcarbonate were added to the coupling and the temperature was raised to80. Para-toluene sulfonyl chloride (22 parts) was added and thetemperature was maintained at 80 for one hour. The mixtnure was saltedwith 15% sodium chloride (wt. based on volume of slurry), and allowed tostir and cool to 50. The crystalline product was filtered. After dryingand grinding, the resultant solid was an orange water-soluble powderhaving the structure:

(Structure 1) and which was found to be useful for dyeing synthetic andnatural polyamide fibers from neutral or weakly acid dyebaths in orangeshades which are fast to light and washing.

Example 2 In Example 1, While otherwise proceeding: as described, thephenol was replaced with 10.8 parts of ortho-cresol,

a affording a similar product to that of Example 1, having similarproperties and having the structure:

SOQH

Example 3 In Example 1, while otherwise proceeding as described, thephenol was replaced with 10.8 parts of meta-cresol,

4 Example 7 In Example 1, while otherwise proceeding as described,

(Structure 2) resulting in an orange dye having similar properties tothe dye of Example 1, and having the structure:

Example 4 In Example 1, while otherwise proceeding as described, thephenol was replaced with 10.8 parts of para-cresol, resulting in anorange dye having similar properties to the dye of Example 1, and havingthe structure:

1 SOTGCI'IS (Structure 4) Example 5 the para toluenesulfony chloride wasreplaced with 24 parts of para-chloro-benzene sulfonyl chloride,resulting in an orange dye having similar properties to that of Example1, and having the structure:

(Structure 7) Example 8 3-amino-4-chlorobenzene sulfonic acid (20.8parts) i C H (Structure 3) was dissolved in 100 parts of water byaddition of 6 parts of sodium carbonate, iced to 0, and diazotized byaddition of parts of concentrated hydrochloric acid and 7 parts ofsodium nitrite as solution. A solution of 14.3 parts ofalpha-naphthylamine dissolved in 300 parts of water and 15 parts ofconcentrated hydrochloric acid at 70 was added together with sufiicientice to maintain the temperature of the coupling at 5-10. Sodiumhydroxide solution was added gradually with good stirring to raise thepH of the coupling to 10 in about 30 minutes. Addition of 8 parts ofsodium nitrite as 30% solution, 50 parts of concentrated hydrochloricacid, and

ice to 5 and stirring for four hours resulted in rediazoti- Zation ofthe coupling. The solid diazoniurn salt was filtered, repasted in waterand ice, treated with 11 parts of 85% phenol and then with 20 parts ofsodium carbonate at 0. The mixture was stirred until coupling wascomplete. It was then treated with 4 parts of sodium hydroxide and 5parts of sodium carbonate, heated to 80 (Structure 5) Example 6 i InExample 1, while otherwise proceeding as described, the para-toluenesulfonyl chloride was replaced with 20 parts of benzene sulfonylchloride, resulting in a dye having similar properties to the dyeprepared in Example 1, but having the structure:

(Structure 6) shades which are fast to light and washing. The productwas water soluble and had the structure:

(Structure 8) 5 6 Example 9 A fabric consisting of 100 parts of nylontricot was The compound havmg structure entered into a dyebath at pH 7.5prepared by dissolving 1 part of the dye of Example 1 in 2000 parts ofwater, and 3. The compound having the structure the fabric was moved inthe bath at 100 for one hour.

At the end of this time nearly all of the orange color had left the bathand dyed the nylon a uniform orange shade.

The dyeing had good properties with respect to washing and lightfastness. 25

I claim: CH 1. A compound having the following structure:

4. The compound having the structure I S0 11 R2 wherein R represents aradical selected from the group 35 5. The compound having the structureconsisting of --H, chloro ortho to the azo linkage, and 6. The compoundhaving the structure s'oaH chloro para to the azo linkage; R and Rrepresent :1 References Cited by the Examiner radical selected from thegroup consisting of H and UNITED STATES PATENTS CH and R represents abenzene sulfonic ester radical fr Selected from the group consisting of2,124,690 7/1938 Daudt et a1. 260-491 X 2,180,246 11/1939 Kresber 260191o goc o so vc d 2,222,749 11/1940 Kresbe'r 260-197 CHARLES B. PARKER,Primary Examiner. 60 FLOYD D. HIGEL, Assistant Examiner.

1. A COMPOUND HAVING THE FOLLOWING STRUCTURE: